No. I invention in the present invention relates to a regeneration of a PET, and it relates to a regenerated PET resin composition in which there is improved a molding processability such as an injection moldability and extrusion processability, and a molded article therefrom. Further, No. II invention in the present invention relates to a thermoplastic resin composition containing a flame retardant and a molded article therefrom, in more detail, it relates to a flame retardant resin composition in which bleeding of the flame retardant is suppressed without a decline of flame retardancy, and a molded article therefrom.
Thermoplastic resins are produced in a large amount because those are light and tough, excellent in water resistance, chemical resistance, and an electric insulation property, and easy in molding and processing. Particularly, a polyethylene terephthalate which is usually called a PET is mass-produced as bottles for beverages because it is light and tough and, further, excellent in transparency. Recently in Japan, Recycling Law for Vessels and Wrapping materials is enforced, and there is proceeded a measure of a shift to a recycling society in relation to plastics. Further, recycling of PET bottles is desired because of a worldwide trend.
However, since the regenerated PET resin includes a problem of a poor moldability, it is difficult to obtain a molded article by an injection molding method which is usually employed for general-purpose resins such as a polyolef in resin. For that reason, there is limited a use of the regenerated PET, and regeneration of PET is not progressed. Further, since the regenerated PET resin is a crushed resin from recollected bottles for beverages, textiles, and films, etc., it is usually unsettled in shapes and a flake-state, whereby, it is bulky and worse in transport efficiency.
Accordingly, it is desired that the regenerated PET resin is pellet-state in consideration of transport efficiency.
However, since moldability is poor, it is difficult to prepare uniform pellets. It is an existing circumstance that there are not methods by which there can be solved the above-described various problems in the regenerated PET resin.
The No. I invention in the present invention aims to provide a regenerated PET resin composition in which there is improved a molding processability such as an injection moldability and extrusion moldability, and to provide a molded article therefrom.
Further, since thermoplastic resins are light and tough, excellent in water resistance, chemical resistance, and an electric insulation property, and easy in molding and processing, those are employed in a wide range such as construction materials, materials for electric equipments, parts for cars, internally decorative materials for cars, covering materials for electric cables, parts for precise machines, other various industrial materials, and household goods, etc. However, since the thermoplastic resins have a drawback of readily burning, there are proposed many methods for flame retardation of the thermoplastic resins. As such the methods for flame retardation, there is a method in which a flame retardant is added to the thermoplastic resins, and which is most popular.
However, the flame retardant resin composition containing the flame retardant includes a problem that the flame retardant oozes out (it is to be noted that oozing out of a liquid flame retardant is occasionally called a bleeding, and oozing out of a solid flame retardant is occasionally called a blooming, however, in the present specification, a phenomenon of oozing out in the flame retardant is merely called bleeding regardless of kinds of the flame retardant) when it is stored at high temperature for a long time of period, and it makes an outer appearance of a final product worse.
Further, since the flame retardant oozes out onto surface of resins by bleeding of the flame retardant, it is becoming problematic from a hygienic viewpoint because the flame retardant adheres to a human body in handling the final product.
A variety of methods are proposed for solving the above-described problems. For example, although there are reported a method (JP-A-06299007 Official Gazette) in which a specified compound is mixed with a polyolefin resin and a method (JP-A-07053796 Official Gazette) in which inorganic fillers are formulated in a crystalline propylene polymer containing a halogen-contained flame retardant and an auxiliary agent for the flame retardant. However, it is an existing circumstance that the both methods are not satisfied in an effect for suppressing bleeding of the flame retardant.
Therefore, the No. II present invention aims to providing a flame retardant resin composition in which bleeding of a flame retardant is suppressed without allowing to lower a flame retardancy, and to providing a molded article therefrom.
Hereinafter, the No. I and No. II inventions are separately illustrated.
The inventors of the present invention, as a result of an intensive investigation for solving the above-mentioned problems in the No. I invention, found out that the above-mentioned problems can be effectively solved by mixing a specified amount of an organic ester compound for regenerating a PET resin, and attained to the invention.
That is, the No. I invention relates to a regenerated PET resin composition which comprises 100 parts by weight of a regenerated PET resin (A) and 0.5-100 part by weight of a lactone polymer (B). The present invention further relates to a regenerated PET resin composition further containing a polyolefin resin (C).
The present invention relates to a regenerated PET resin composition further containing other additives (D) composed of an inorganic compound or an organic compound. The present invention relates to a regenerated PET resin molded article which comprises molding the regenerated PET resin composition.
The inventors of the present invention, as a result of an intensive investigation for solving the above-mentioned problems in the No. II invention, found out that the above-mentioned problems can be effectively solved by mixing a specified amount of a polyester resin, and attained to the invention.
That is, the No. II-1 of the invention (hereinafter, referred to xe2x80x9cII-1 inventionxe2x80x9d) relates to a flame retardant resin composition in which there are contained 100 parts by weight of a thermoplastic resin and 0.5-100 part by weight of a flame retardant which comprises mixing 100 parts by weight of a flame retardant (F) with 1-200 part by weight of a mixture composed of a polyester resin (G) and an ester compound (H) of a polyglycerine or glycerine with a higher fatty acid. Further, it relates to a flame retardant resin composition further containing an additive (I) consisting of at least one inorganic compounds, organic compounds, or other additives for resins in the above-described composition. Still further, it relates to a flame retardant resin composition in which a mixing weight ratio is (G):(H)=85-99.5:0.5-15 (total of both weight ratio is 100) in a mixture composed of the above-described polyester resin (G) and ester compound (H) of a polyglycerine or glycerine with a higher fatty acid.
Particularly, it relates to a flame retardant resin composition in which the flame retardant (F) is composed of at least any one kind of a bromine-based flame retardant, a chlorine-based flame retardant, a phosphorus-based flame retardant, a phosphate-based flame retardant, a polyphosphoric acid-based flame retardant, a nitrogen compound-based flame retardant, or an inorganic-based flame retardant. Further, it relates to a resin composition in which the polyester resin (G) is an aliphatic or aromatic polyester resin. Still further, it relates to a resin composition in which the aliphatic polyester resin is a lactone polymer (B).
Also, it relates to a flame retardant resin composition in which the ester compound (H) of a polyglycerine or glycerine with a higher fatty acid is at least any one of a monoglyceride, diglyceride, triglyceride, a diglycerine fatty acid ester, a triglycerine fatty acid ester, a tetraglycerine fatty acid ester, a pentaglycerine fatty acid ester, a hexaglycerine fatty acid ester, and a decaglycerine fatty acid ester. Further, the present invention relates to a flame retardant resin molded article which comprises molding any one of the above-described flame retardant resin compositions.
The No. II-2 of the invention (hereinafter, referred to xe2x80x9cII-2 inventionxe2x80x9d) relates to a flame retardant resin composition in which 1-200 parts by weight of a polyester resin (G) is mixed with 100 parts by weight of the flame retardant (F) in the flame retardant resin composition containing 100 parts by weight of the thermoplastic resin (E) and 0.5-100 parts by weight of the flame retardant (F). Further, it relates to a flame retardant resin composition in which the above-described composition is mixed with other additives (I) composed of at least any one of inorganic or organic compound, or other additives for resins.
Particularly, it relates to a flame retardant resin composition in which the above-described flame retardant (F) is composed of at least any one kind of a bromine-based flame retardant, a chlorine-based flame retardant, a phosphorus-based flame retardant, a phosphate-based flame retardant, a phosphoric acid-based flame retardant, a nitrogen compound-based flame retardant, or an inorganic-based flame retardant. Further, it relates to a flame retardant resin composition in which the above-described polyester resin (G) is an aromatic or aliphatic polyester resin. Also, it relates to a flame retardant resin composition in which the aliphatic polyester resin is a lactone polymer. Still further, it relates to a flame retardant resin molded article molded from the flame retardant resin composition.
The No. II-3 of the invention (hereinafter, referred to xe2x80x9cII-3 inventionxe2x80x9d) relates to a flame retardant polyolefin resin composition which comprises mixing 1-30 parts by weight of a polyester resin (G) is mixed with 100 parts by weight of the resin composition composed of 100 parts by weight of a polyolefin resin (P) and 0.2-40 parts by weight of a halogen-based flame retardant (FD). Further, it relates to a flame retardant polyolefin resin composition further containing other additives (I) composed of at least any one of inorganic or organic compound, or other additives for resins. Also, it relates to a flame retardant polyolefin resin composition in which the halogen-based flame retardant (FD) in the above-described invention is an organic compound containing a halogen. Also, it relates to a flame retardant polyolefin resin composition in which the organic compound containing a halogen is a phosphate containing a halogen. Also, it relates to a flame retardant polyolefin resin composition in which the polyester resin (G) in the above-described invention is an aromatic or aliphatic polyester resin. And also, it relates to a flame retardant polyolefin resin molded article having a flame retardancy which comprises molding a flame retardant polyolef in resin composition in which the aliphatic polyester resin is a lactone polymer (B) and the above-described polyolefin resin composition.
The No. II-4 of the invention (hereinafter, referred to xe2x80x9cII-4 inventionxe2x80x9d) relates to a flame retardant resin composition containing 100 parts by weight of a thermoplastic resin (E) and 0.2-40 parts by weight of a flame retardant (F) in which 0.5-50 parts by weight of an ester compound (H) of a polyglycerine or glycerine with a higher fatty acid is mixed with 100 parts by weight of a flame retardant (F). It relates to a flame retardant resin composition which comprises further containing additives (r) composed of at least any one kinds of inorganic compounds, organic compounds, and other additives for resins. Particularly, it relates to a flame retardant resin composition in which the above-described flame retardant (F) is composed of at least any one kind of a bromine-based flame retardant, a chlorine-based flame retardant, a phosphorus-based flame retardant, a phosphate-based flame retardant, a polyphosphoric acid-based flame retardant, a nitrogen compound-based flame retardant, or an inorganic-based flame retardant. Further, it relates to flame retardant resin composition in which the ester compound (H) of a polyglycerine or glycerine with a higher fatty acid is at least any one of a monoglyceride, diglyceride, triglyceride, a diglycerine fatty acid ester, a triglycerine fatty acid ester, a tetraglycerine fatty acid ester, a pentaglycerine fatty acid ester, a hexaglycerine fatty acid ester, and a decaglycerine fatty acid ester. Further, other means in the present invention relates to a flame retardant resin molded article which comprises molding any one of the above-described respective flame retardant resin compositions.
Hereinafter, embodiments for carrying out the Nos. I and II inventions are illustrated in order.
The No. I invention is illustrated.
 less than Regenerated PET Resin (A) greater than 
The PET to be employed in the present invention is an abbreviation of a polyethylene terephthalate, and it is a resin obtained by a polymerization reaction of a glycol ester of terephthalic acid until a fixed polymerization degree under the presence of a catalyst, and the glycol ester is obtained by a thermal reaction under the presence of a catalyst using terephthalic acid or an ester-formable derivative (for example, a lower alkyl ester such as a dimethyl ester and monoester) and ethylene glycol or the ester-formable derivative as starting raw materials.
The regenerated PET resin (A) in the present invention means a resin recycled and treated in order to utilize after the PET was molded and used as a product such as bottles for beverages, textiles, films, and a large-sized molded article such as container, and it is usually called a regenerated PET materials or a recycled PET. The regenerated PET resin (A) to be employed in the present invention is not limited to a product form of a PET to be regenerated and, specifically, there can be exemplified bottles for beverages, textiles, films, and a molded article, etc. Further, it also includes a PET material such as chips of films and gates or runners in injection-molded articles which are produced in the preparation of final products, even though those are not employed as the final products.
 less than Lactone Polymer (B) greater than 
The lactone polymer (B) to be employed in the present invention can be obtained by a ring-opening polymerization of a lactone having a carbon number of 4-11. Specifically, a poly-xcex5-caprolactone is preferred. Further, there can be employed a copolymer in which there are employed comonomers such as valerolactone, glycolide, and lactide other than xcex5-caprolactone monomer.
As a lactone polymer other than the above-described ones, there may be also employed a polycaprolactone in which terminal groups are capped.
The lactone polymer (B) in the present invention is obtained by a continuous or batchwise reaction at 120-230xc2x0 C., preferably 140-220xc2x0 C. while agitating for several hours, in which a polymerization initiator is added to a lactone monomer and, preferably, and a catalyst is optionally employed.
The polymerization initiator to be employed in the preparation of a lactone polymer (B) described in the present invention is water or a compound having hydroxyl groups at terminals and, as the compound having hydroxyl groups at terminals, there can be exemplified, for example, a monovalent alcohol such as n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, lauryl alcohol, and mylistyl alcohol, glycols such as ethylene glycol, propylene glycol, ethylethylene glycol, 1,4-butanediol, 2,3-butylene glycol, 2-methyl-1,2-propane diol, pinachol, xcex2-butylene glycol, diethylene glycol, pentamethylene glycol, tetramethylene glycol, neopentyl glycol, and 1,4-cyclohexane dimethanol, trivalent alcohols such as glycerine, 1,2,3-butane triol, 1,2,3-pentane triol, trimethylol propane, and ditrimethylol propane, or derivatives thereof, tetravalent alcohols such as erythrit and pentaerythritol, aromatic alcohols such as phenol, bisphenol A, 2,4,6-tribromophenol, and tetrabromobisphenol A, monovalent carboxylic acids such as benzoic acid, p-methyl benzoic acid, lauric acid, myristic acid, 2,3,4-tribromobenzoic acid, pentabromobenzoic acid, divalent carboxylic acids such as isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4xe2x80x2-diphenoxyethane dicarboxylic acid, succinic acid, adipic acid, sebasic acid, azelaic acid, decadicarboxylic acid, cyclohexane dicarboxylic acid, tetrachlorophthalic acid, and tetrabromophthalic acid, trivalent carboxylic acids such as tricarbaryl acid, trimerysic acid, and trimeritic acid, tetravalent carboxylic acids such as pyromeritic acid, oxycarboxylic acids such as xcex5-oxycarboxylic acid and hydroxyethoxy benzoic acid, etc. Further, as the catalyst for the polymerization, there can be employed a variety of organic or inorganic metal compounds, etc. and, specifically, there can be enumerated tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, dibutyltin oxide, dibutyltin laurate, stannous octylate, and stannous chloride, etc. Use amount of the catalysts is 0.1-1,000 ppm, and preferably 0.5-500 ppm based on starting raw materials.
A molecular weight of the lactone polymer (B) to be employed in the present invention is 1,000-500,000, preferably 5,000-200,000, and more preferably 10,000-100,000 as a number average molecular weight.
In the case that the number average molecular weight is less than 1,000, there is not shown an effect for improving a molding processability of the regenerated PET resin and, in the case of more than 500,000, it cannot be melt-kneaded into the regenerated PET resin. The number average molecular weight described herein is a number average molecular weight measured using a liquid chromatograph.
 less than Polyolefin Resin (C) greater than 
The polyolef in resin (C) to be employed in the composition of the present invention can be freely selected from an olef in polymer such as a low density polyethylene, a high density polyethylene, a linear-state polyethylene, a polybutadiene, a polypropylene, a poly-1-butene, a poly-1-pentene, a poly-4-methyl-1-pentene, and a mixture thereof, an ethylene-vinyl acetate copolymer, a copolymer of ethylene, propylene, 1-butene, 1-pentene, and a mixture thereof, a polyolefin-based elastomer such as an ethylene-propylene rubber (EPM, EPR), an ethylene-propylene-diene terpolymer (EPDM, EPD, EPT), and a mixture thereof, a mixture of the polyolefin-based elastomer with an olefin polymer such as polyethylene, a polypropylene, and an ethylene-propylene copolymer, a copolymer of other vinyl-based monomer primarily containing an olefin, or a mixture of two or more kinds of the above-described ones, and it includes a polyolefin resin (P) which is employed in the No. II invention described hereinafter.
 less than Additives (D) greater than 
In the composition of the present invention, as the other additives (D), there can be mixed the inorganic compounds, the organic compounds, or the other additives for resins, etc.
As the additives for resins, there are enumerated a stabilizer, a coloring agent, a weatherability agent (an ultraviolet ray absorbent), a lubricant, an antistatic agent, an extender, and other additives. There can be also added to the polyolefin resin (C) in addition to a case of being originally contained in the regenerated PET resin.
 less than Formulating Amount of Respective Components greater than 
In the regenerated PET resin composition of the present invention, 0.5-100 parts by weight of a lactone polymer (B) is preferably formulated based on 100 parts by weight of a regenerated PET resin (A), and 1-20 parts by weight of a lactone polymer (B) is more preferably formulated based on 100 parts by weight of a regenerated PET resin (A). In the case that the lactone polymer (B) is less than 0.5 part by weight, there is not shown an effect for improving a molding processability of the regenerated PET resin composition and, in the case of more than 100 parts by weight, there is caused a disadvantage of decline in a strength of a molded article. Formulation of 1-20 parts by weight in the lactone polymer (B) is particularly effective in a viewpoint of an improvement of moldability.
The polyolefin resin (C) is preferably formulated in 1-100 parts by weight, preferably 20-100 parts by weight based on 100 parts by weight of a regenerated PET resin. By the formulation of the polyolef in resin (C), although there is shown an effect that moldability is improved, in the case of less than 1 part by weight, there is not shown an effect that moldability is improved and, on the other hand, in the case of more than 100 parts by weight, strength of a molded article tends to lower.
 less than Method for the Preparation and Method for Molding of the Regenerated PET Resin Composition greater than 
The composition of the present invention is usually prepared by publicly-known methods. For example, there is enumerated a method in which there are melt-kneaded the regenerated PET resin (A), the lactone polymer (B), and optionally, the polyolefin resin (C) and other additives (D) in an extruder, a kneader, a roll, and a Banbury mixer, or a method in which particle-state substances are mechanically and uniformly mixed each other, and then, molding is conducted together with mixing in an injection molding machine.
Although thus-obtained regenerated PET resin composition may be once extruded to prepare pellets, preferably, it is simultaneously or subsequently molded to prepare a molded article by an extrusion molding, an injection molding, and compression molding, etc. together with mixing. The molded article is also excellent in heat resistance and an electric insulation property in addition to mechanical properties.
 less than Uses of the Regenerated PET Resin Composition greater than 
The regenerated PET resin composition of the present invention can be employed for a variety of molded articles in place of conventional thermoplastic resins. For example, it is useful for home electric appliances, specifically, a cover for a refrigerator, a condenser cover for a washer, a backside cover for a TV, a speaker box for a TV, a deflecting york for a TV, a plug and socket, a socket for a christmas light, a CRT monitor body, an impeller in a blowing outlet for an air conditioner, a wind-direction plate and a cover for a body, a cover for a moisture conditioner, a door for a microwave oven, a seat for a water closet and a hot water tank, a motor cover and a control panel for an electric fan, a connector, a toner box for a PPC, a cover for a ventilating fan, materials for civil engineering and construction, specifically, a trough, a cover for buried electric cables, a pipe cover, monofilaments for flat yarns and a laminate film, a chair and backside cover in an athletic field, a flower pot for plants, an OA floor, materials for cars, specifically, a corrugate tube for electric cables, a floor mat, a door rim, a seat and a lining for a trunk room, a battery case, a cooling fan for a radiator, a protecting plate in an engine room, an instrument panel, a trim for internal decoration, a globe box, a console box, a fan shroud, a housing for an air cleaner, a seat frame, a connector, an ash tray, others, a PP band, a variety of connectors, a pallet, a container, and tray, etc.
Hereinafter, a mode for carrying out the No. II invention is illustrated.
Constructing components shown hereinafter are commonly employed in the (2-1)-(2-4) inventions.
 less than Thermoplastic Resin (E) greater than 
The thermoplastic resin (E) to be employed in the present invention is not particularly limited, if it is melted by heating and solidified again by cooling and it is a resin having a property in which melting and solidification can be reversibly repeated.
Specifically, the thermoplastic resin includes a polyolefin resin (P) described as a constructing component in the No. I invention, and there can be enumerated a vinyl chloride-based resin such as a vinyl chloride, a vinylidene chloride, a vinyl chloride copolymer, for example, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene copolymer, a copolymer in which vinyl chloride is grafted on an ethylene-vinyl acetate copolymer, a polystyrene, a styrene-based resin such as an acrylonitrile-butadiene-styrene copolymer, an acrylic-based resin, engineering plastic resins such as a polycarbonate, a polyethylene terephthalate, a polybutylene terephthalate, a polyphenylene oxide, and a polyphenylene sulphide, etc.
Further, there is also included a resin containing at least one of the above-described various polymers.
 less than Flame Retardant (F) greater than 
The flame retardant (F) in the present invention is not particularly limited, if it is a substance which is added for giving a flame retardancy to resins. Specifically, it is a halogen-contained organic compound and a phosphorus-contained organic compound and, which has at least one halogen in the molecule. As the flame retardant (F) which is added for giving a flame retardancy to resins, for example, there can be enumerated a bromine-based flame retardant such as decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, hexabromocyclododecane, bis(2,4,6-tribromophenoxy)ethane, ethylenebistetrabromophthalic imide, hexabromobenzene, polydibromophenyleneoxide, terabromobisphenol-S, 1,1-sulphonyl[3,5-dibromo-4-(2,3-dibromopropoxy)]benzene, tris(2,3-dibromopropyl-1)isocyanurate, tribromophenol, tribromophenyl allylether, tribromoneopentyl alcohol, a brominated polystyrene, a brominated polyethylene, terabromobisphenol-A, a terabromobisphenol-A-epoxy oligomer, a terabromobisphenol-A-carbonate oligomer, terabromobisphenol-A-bis(2-hydroxydiethylether), terabromobisphenol-A-bis(2,3-dibromopropylether), terabromobisphenol-A-bis(allylether), tetrabromocyclooctane, ethylenebistetrabromophthalic imide, ethylenebispentabromodiphenyl, a poly(pentabromobenzyl polyacrylate), and octabromotrimethylphenyl indane, a chlorine-based flame retardant such as a chlorinated paraffin and perchlorocyclopentadecane, and, as a halogen-contained phosphate, for example, there can be enumerated tris(2,3-dibromopropyl)phosphate, tris(2,3-bromochloropropyl)phosphate, tris(tribromoneopentyl)phosphate, and bis(2,3-dibromopropyl)phosphate)2,3-dichloropropylphosphate, etc.
Further, there can be enumerated a phosphate-based flame retardant such as trisphenyl phosphate, tricresyl phosphate, triethyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl phosphate, lesorcinolbis(diphenyl phosphate), trixylenylphosphate, trimethylphosphate, trimethyl phosphate, 2-ethylhexyl diphenylphosphate, dimethyl phosphate, triallyl phosphate, cresyl-2,6-xylenyl phosphate, bisphenol-A-bis(diphenyl phosphate), bisphenol-A-bis(dicresyl phosphate), tris(chloroethyl)phosphate, trisdichloropropyl phosphate, tris-xcex2-chloropropyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphate, and tris(2,6-dimethylphenyl)phosphate, a phosphorus-based flame retardant such as red phosphorus (usually coated by a phenol resin, etc. in order to stabilize red phosphorus), a polyphosphoric acid-based flame retardant such as polyphosphoric acid ammonium amide, melamine pyrophosphate, and melamine polyphosphate, a nitrogen compound-based flame retardant such as melamine cyanurate, and a inorganic-based flame retardant such as magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentaoxide, zinc hydroxy stannate, zinc stannate, metastannic acid, tin oxide, zinc oxide, ferric oxide, ferrous oxide, stannic oxide, and stannous oxide, etc.
Preferably, there are terabromobisphenol-A, terabromobisphenol-A-bis(2,3-dibromopropylether), tris(tribromoneopentyl)phosphate, 1,1-sulphonyl[3,5-dibromo-4-(2,3-dibromopropoxy)]benzene, decabromodiphenyl oxide, perchlorocyclopentadecane, ethylenebispentabromodiphenyl, octabromotrimethylphenyl indane, hexabromocyclododecane, red phosphorus, trisphenyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl phosphate, lesorcinolbis(diphenyl phosphate), trixylenylphosphate, cresyl-2,6-xylenyl phosphate, bisphenol-A-bis(diphenyl phosphate), bisphenol-A-bis(dicresylphosphate), melamine cyanurate, and polyphosphoric acid ammonium amide, etc.
These flame retardants can be employed in at least any one kind. Also, of those, as the halogen-based flame retardant, there are preferred terabromobisphenol-A, terabromobisphenol-A-bis(2,3-dibromopropylether), tris(tribromoneopentyl)phosphate, 1,1-sulphonyl[3,5-dibromo-4-(2,3-dibromopropoxy)]benzene, and decabromodiphenyl oxide and, particularly, preferably, terabromobisphenol-A-bis(2,3-dibromopropylether) and 1,1-sulphonyl[3,5-dibromo-4-(2,3-dibromopropoxy)]benzene, and ethylenebispentabromodiphenyl, etc. The halogen-contained organic compounds and phosphorus-contained organic compounds can be employed in at least any one kind.
 less than Polyester Resin (G) greater than 
In the present invention, the polyester resin (G) is employed as one component in improvers. As the polyester resin (G), there are employed the lactone polymer (B) illustrated in the No. I invention, an aliphatic or aromatic polyester resin obtained by a condensation reaction of an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sberic acid, azelaic acid, and dodecanoic acid, or an aromatic dicarboxylic acid such as terephtahlic acid, isophtahlic acid, and orthophtahlic acid with an aliphatic diol such as ethylene glycol, 1,3-propane diol, 1,4-butane diol, neopentyl glycol, 1,5-pentane diol, 3-methyl-1,5-pentane diol, 1,6-hexane diol, and 1,9-nonane diol, a cycloaliphatic diol such as cyclohexane-1,4-dimethanol, and an ether-based diol, such as tetramethylene glycol, a lactone-modified polyester resin made from a copolymerization of a polyester resin with lactones, a resin polymerized from a hydroxycarboxylic acid, a copolymerized resin of 3-hydroxybutylate with hydroxycarboxylic acids such as 3-hydroxyvalirate, and a mixture thereof.
The aliphatic or aromatic dicarboxylic acids may be employed in combination of two or more kinds. Also, the diols can be employed in combination of two or more kinds. Of those, preferred polyester resin is the lactone polymer (B), specifically, a poly-xcex5-caprolactone is preferred. Further, in addition to xcex5-caprolactone monomer, a copolymer can be also employed, in which there are employed comonomers such as valerolactone, glycolide, and lactide.
In the polyester resin (G) to be employed in the present invention, a molecular weight is 1,000-500,000, preferably 5,000-200,000 and, more preferably 30,000-100,000 as a number average molecular weight. In the number average molecular weight is less than 1,000, an effect for preventing bleeding is not obtained in the flame retardants and, in the case of more than 500,000, it cannot be melt-kneaded into the thermoplastic resins. The number average molecular weight shown herein is a number average molecular weight measured by a liquid chromatography.
The preparation of the lactone polymer (B) is as shown in the descriptions concerning the preparation of the lactone polymer (B) and the polymerization initiators in the No. I invention.
The aliphatic or aromatic polyester resins can be prepared by publicly-known methods.
For example, it can be obtained by a method in which a lower alcohol ester of the dicarboxylic acid is transesterified with an excess amount of a glycol under the presence of a catalyst to obtain a reaction product, and the reaction product is polycondensed, or a method in which the dicarboxylic acid is esterified with an excess amount of a glycol under the presence of a catalyst to obtain a reaction product, and it is polycondensed. Reaction temperature is 180-290xc2x0 C., and preferably 200-280xc2x0 C.
As the catalysts for polymerization, there can be enumerated a titanium compound, an antimony compound, a tin compound, a calcium compound, and a manganese compound, etc. Use amount of the catalysts is 0.1-1,000 ppm, and preferably 0.5-500 ppm based on starting raw materials.
 less than Ester Compound (H) greater than 
In the present invention, as another component of the improvers, the ester compound (H) is employed which is synthesized from a polyglycerine or glycerine and a higher fatty acid. One raw material for the ester compound (H) is a polyglycerine or glycerine, and the polyglycerine is a polymer of glycerine. As the polyglycerine, there can be enumerated diglycerine, triglycerine, tetraglycerine, pentaglycerine, hexaglycerine, and decaglycerine, etc.
In the present invention, the higher fatty acid is a long chain fatty acid, which is employed as another raw materials for the ester compound (H). Specifically, there are exemplified a saturated fatty acid such as stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, and erucic acid, an unsaturated fatty acid such as oleic acid, behenic acid, and linoleic acid, a hydroxy fatty acid such as sabinic acid, iproic acid, yarapinol acid, uniperic acid, anbletol acid, aluit acid, camloreic acid, feronic acid, celeblonic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyhexadecanoic acid, 12-hydroxystearic acid, 18-hydroxyoctadecanoic acid, and 9,10-dihydroxyoctadecanoic acid, and those are utilized solely or as a mixture of two or more kinds.
The ester compound (H) in the present invention is synthesized by the above-described raw materials, and a synthesis method and an esterification degree (addition amount of the fatty acid) are not particularly limited. As the ester compound (H) in the present invention, there are specifically exemplified a monoglyceride, a diglyceride, a triglyceride, a fatty acid ester of diglycerine, a fatty acid ester of triglycerine, a fatty acid ester of tetraglycerine, a fatty acid ester of pentaglycerine, a fatty acid ester of hexaglycerine, and a fatty acid ester of decaglycerine, etc., and the ester compound (H) is constructed solely or in combination of two or more kinds.
 less than Other Additives (I) greater than 
The other additives (I) is composed of at least one of an inorganic compound, an organic compound, and other additives for resins, and it is the same as in the additives (D) in the No. I invention. As the additives for resins, there are enumerated a stabilizer, a coloring agent, a weatherability agent (an ultraviolet ray absorbent), a lubricant, an antistatic agent, an extender, and other additives, and these may be also added to the thermoplastic resin (E), for example, a polyolefin resin. As the inorganic compound which is the additives (I), in addition to fillers for resins, there can be employed other kinds of flame retardants except ones employed as the (F). As auxiliary agent for the flame retardant, there may be employed other kinds of flame retardants, for example, an antimony oxide such as antimony trioxide and antimony pentaoxide and, in the case, use amount of the halogen-based flame retardant (FD) may be smaller amount.
As the thermoplastic resin which is one of the additives (I), if it is compatible with the flame retardant polyolef in resin composition of the present invention, it can be particularly employed without any limitations.
 less than Formulating Amount of Respective Components greater than 
The flame retardant resin composition of the II-1 invention contains 0.5-100 parts by weight of the flame retardant (F) with respect to 100 parts by weight of the thermoplastic resin (E).
In the case that the flame retardant (F) is less than 0.5 part by weight, a flame retardant property is insufficient in a composition obtained and, in the case of exceeding 100 parts by weight, strength lowers in a composition, resulting in that there is caused a problem that there lower molding processability and pelletizing processability.
In the present invention, addition amount of a mixture composed of the polyester resin (G) and the ester compound (H) of a polyglycerine or glycerine with a higher fatty acid is 1-200 parts by weight based on 100 parts by weight of the flame retardant (F).
In the case that the addition amount of a mixture composed of the polyester resin (G) and the ester compound (H) is less than 1 part by weight based on 100 parts by weight of the flame retardant (F), there cannot be obtained an effect for preventing bleeding and, in the case of exceeding 200 parts by weight, physical properties and pelletizing processability unpreferably lower in a composition.
Further, in the mixture composed of the polyester resin (G) and the ester compound (H), mixing ratio by weight of (G):(H) is preferably 85-99.5:0.5-15 (total amount of both is 100). In the case that the addition amount of the ester compound (H) is less than 0.5 weight ratio, there is not shown an effect for improving a bleeding property in a final product for a long time of period and, in the case of exceeding 15 weight ratio, a bleeding property is obstructed in a final product, and further, and a flame retardancy lowers in the resin composition itself.
In the composition of the present invention, other additives (I) can be optionally employed, and these can be in advance added to the thermoplastic resin (E).
 less than Examples of a Flame Retardant Resin Composition greater than 
In the present invention, formulation of the mixture in which the polyester resin (G) is mixed with the ester compound (H) shows an effect for preventing bleeding of a phosphate, preferably, trisphenyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl phosphate, lesorcinolbis(diphenyl phosphate), trixylenyl phosphate, cresyldi-2,6-xylenyl phosphate, bisphenol-A-bis(diphenylphosphate), and bisphenol-A-bis(dicresylphosphate).
For that reason, it is useful as an anti-bleeding agent for the phosphates.
Further, in the case that a phosphate such as trisphenyl phosphate is employed in flame retardant resin compositions described hereinafter, there is particularly shown an effect for preventing bleeding.
1. Resin composition composed of (a) a polystyrene, (b) a polyphenylene oxide, (c) a phosphate-based flame retardant such as trisphenyl phosphate, and (d) a melamine isocyanurate.
2. Resin compositioncomposedof (a) apolycarbonate, (b) an ABS resin, and (c) a phosphate-based flame retardant such as trisphenyl phosphate.
Accordingly, the mixture composed of the polyester resin (G) and the ester compound (H) is desirably added as an anti-bleeding agent in the flame retardant resin compositions. Also, in a resin composition in which the mixture composed of the polyester resin (G) and the ester compound (H) is desirably added as an anti-bleeding agent in the flame retardant resin compositions, the flame retardant does not bleed, and it is useful as a resin composition in which a flame retardancy is given.
 less than Method for the Preparation of the Flame Retardant Resin Composition greater than 
The composition of the present invention is usually prepared by publicly-known methods. For example, there are enumerated a method in which there are melt-kneaded the thermoplastic resin (E), the flame retardant (F), the polyester resin (G), the ester compound (H) of a polyglycerine or glycerine with a higher fatty acid, and other additives (I) in an extruder, a kneader, a roll, and a Banbury mixer, or a method, etc. in which particle-state substances are mechanically and uniformly mixed each other, and then, molding is conducted together with mixing in an injection molding machine. Further, although a mixing order may be voluntary in the case, it is a preferred method that there are premixed the flame retardant (F), the polyester resin (G), and the ester compound (H), followed by mixing a mixture into a resin, and mixing method of respective components can be appropriately changed.
 less than Molding Method of the Flame Retardant Resin Composition greater than 
Although thus-obtained flame retardant resin composition is subsequently molded to prepare a molded article by an extrusion molding, an injection molding, and compression molding, etc. together with mixing. The molded article is also excellent in flame retardancy, heat resistance and an electric insulation property in addition to mechanical properties and, in which the flame retardant does not bleed, and outer appearance is also excellent.
 less than Uses of the Flame Retardant Resin Composition greater than 
The flame retardant resin composition of the present invention can be employed for a variety of molded articles in place of conventional thermoplastic resins containing a flame retardant (F). For example, it is useful for home electric appliances, specifically, a cover for a refrigerator, a condenser cover for a washer, a backside cover for a TV, a speaker box for a TV, a deflecting york for a TV, a plug and socket, a socket for a Christmas light, a CRT monitor body, an impeller in a blowing outlet for an air conditioner, a wind-direction plate and a cover for a body, a cover for a moisture conditioner, a door for a microwave oven, a seat for a water closet and a hot water tank, a motor cover and a control panel for an electric fan, a connector, a toner box for a PPC, a cover for a ventilating fan, materials for civil engineering and construction, specifically, a trough, a cover for buried electric cables, a pipe cover, monofilaments for flat yarns and a laminate film, a chair and back cover in an athletic field, a flower pot for plants, an OA floor, materials for cars, specifically, a corrugate tube for electric cables, a floor mat, a door rim, a seat and a lining for a trunk room, a battery case, a cooling fan for a radiator, a protecting plate in an engine room, an instrument panel, a trim for internal decoration, a glove box, a console box, a fan shroud, a housing for an air cleaner, a seat frame, a connector, an ash tray, others, a PP band, a variety of connectors, and a pallet, etc.
The flame retardant resin composition of the II-2 invention comprises formulating 1-200 parts by weight of the polyester resin (G) based on 100 parts by weight of the flame retardant (F), in the flame retardant resin composition containing 0.5-100 parts by weight of the flame retardant (F) based on 100 parts by weight of the thermoplastic resin (E). In the case that the flame retardant (F) is less than 0.5 parts by weight, a flame retardancy is insufficient in a composition obtained and, in the case of exceeding 100 parts by weight, a strength lowers in a composition, resulting in that there is caused a disadvantage that there lower molding processability and pelletizing processability.
In the present invention, addition amount of the polyester resin (G) is 1-200 parts by weight based on 100 parts by weight of the flame retardant (F). In the case that the addition amount of the polyester resin (G) is less than 1 part by weight with respect to the flame retardant, there cannot be obtained an effect for preventing bleeding and, in the case of exceeding 200 parts by weight, physical properties and pelletizing processability unpreferably lower in a composition. Further, in the composition of the present invention, other additives (I) can be optionally employed, and these can be in advance added to the thermoplastic resin (E).
 less than Examples of the Flame Retardant Resin Composition of the No. II-2 Invention greater than 
In the present invention, the polyester resin (G) shows an effect for preventing bleeding when there are employed a phosphate, preferably, trisphenyl phosphate, cresyldiphenyl phosphate, xylenyldiphenyl phosphate, lesorcinolbis(diphenyl phosphate), trixylenylphosphate, cresyldi-2,6-xylenylphosphate, bisphenol-A-bis(diphenyl phosphate), and bisphenol-A-bis(dicresyl phosphate) as the flame retardant (F). For that reason, it is useful as an anti-bleeding agent for the phosphates.
Further, by the use of a phosphate such as trisphenyl phosphate, there is particularly shown an effect for preventing bleeding in the same resin composition as in a flame retardant resin composition illustrated in the No. II-1 invention.
That is, 1. Resin compositioncomposedof (a) apolystyrene, (b) a polyphenylene oxide, (c) a phosphate-based flame retardant such as trisphenyl phosphate, and (d) a melamine isocyanurate.
2. Resin composition composed of (a) a polycarbonate, (b) an ABS resin, and (c) a phosphate-based flame retardant such as trisphenyl phosphate.
Accordingly, the polyester resin (G) is desirably added as an anti-bleeding agent in the above-described flame retardant resin compositions. Also, in a resin composition in which the polyester resin (G) in the present invention is added, the flame retardant does not bleed, and it is useful as a resin composition in which a flame retardancy is given.
Method for the preparation of the flame retardant resin composition of the No. II-2 invention is according to the II-1 invention. Addition order may be free, and there is also a desired method in which the flame retardant (F) is premixed with the polyester resin (G), followed by mixing with a resin. Method for molding of the flame retardant resin composition of the invention and uses thereof are also according to the II-1 invention.
The flame retardant polyolefin resin composition of the II-3 invention comprises mixing 1-30 parts by weight of a polyester resin (G) is mixed with 100 parts by weight of the resin composition composed of 100 parts by weight of a polyolefin resin (P) and 0.2-40 parts by weight of a halogen-based flame retardant (FD). In the case that the halogen-based flame retardant (FD) is less than 0.2 part by weight, a flame retardant property is insufficient in a composition obtained and, in the case of exceeding 40 parts by weight, there is caused a disadvantage that a physical property, particularly, strength unpreferably lowers in a composition.
Herein, the polyolef in resin (P) is one of resins which construct the above-described thermoplastic resin composition (E), and it is as descriptions illustrated hereinabove. Further, the halogen-based flame retardant (FD) is one of the above-described flame retardant (F), and it is as descriptions illustrated hereinabove.
In the present invention, addition amount of the polyester resin (G) is 1-30 parts by weight based on 100 parts by weight of the resin composition comprising the polyolef in resin (P) and the halogen-based flame retardant (FD). In the case that the addition amount of the polyester resin (G) is less than 1 part by weight, there cannot be obtained an effect for preventing bleeding and, in the case of exceeding 30 parts by weight, physical properties and pelletizing processability unpreferably lower in a composition.
Further, in the polyolefin resin composition of the present invention, other additives (I) can be optionally employed, and these can be in advance added to the polyolefin resin (P)
A method for the preparation of the flame retardant polyolefin resin is according to the II-1 invention. Addition order may be free, and there is also a desired method in which the halogen-based flame retardant (FD) is premixed with the polyester resin (G), followed by mixing with a resin.
Further, a method for molding of the flame retardant resin composition of the invention and uses thereof are also according to the II-1 invention.
The flame retardant resin composition of the No. II-4 invention comprises formulating 100 parts by weight of a thermoplastic resin (E) and 0.2-40 parts by weight of a flame retardant (F) in which 0.5-50 parts by weight of an ester compound (H) of a polyglycerine or glycerine with a higher fatty acid is mixed with 100 parts by weight of a flame retardant (F). In the case that the flame retardant (F) is less than 0.2 part by weight, there cannot be obtained an effect for preventing bleeding in a composition obtained and, in the case of exceeding 40 parts by weight, there is caused a disadvantage that a physical property, particularly, strength unpreferably lowers in a composition.
In the present invention, addition amount of the ester compound (H) is 0.5-50 parts by weight with respect to 100 parts by weight of the flame retardant (F).
In the case that the addition amount of the ester compound (H) is less than 0.5 part by weight, there cannot be obtained an effect for preventing bleeding and, in the case of exceeding 50 parts by weight, there is caused a disadvantage that a physical property and pelletizing processability unpreferably lowers in a composition.
In the composition of the present invention, other additives (I) can be optionally employed, and these can be also in advance added to the thermoplastic resin (E).
Method for the preparation of the flame retardant resin composition is according to the II-1 invention. Addition order may be free, and there is also a desired method in which the flame retardant (F) is premixed with the ester compound (H) and optionally, the other additives (I), followed by mixing with a resin. Method for molding of the flame retardant resin composition of the invention and uses thereof are also according to the II-1 invention.